Azo-dyestuffs containing chromium and process of making same



Patent ed Nov. 22, 1932 FRITZ STRAUB, WALTER .ANDERAU, AND HANS PATENTfoFFlcE MAYER, on BASEL, SWITZERLAND,

ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, 0F BASEL,SWITZERLAND I AZO-DYESTUFFS CONTAINING GI'IROMIUM AND PROCESS OFMAKINGSAME.

No Drawing. Application, filed April 11, 1928, Serial No. 269,293, andin Ewitzerland .Aiiri1 23,'1927,

The present invention relates to new dyestuffs containing chromium. Itcomprises the new azo-dyestuffs, the process of making same, and thematerial dyed with the new dyestuffs.

It has been found that new valuable dyestuffs are obtained by treatingwith agents yielding chromium such as o-hydroxy-az odyestuffs which areobtained by uniting diazotized 2-amino-1-hydr0xybenzene of the generalformula N02; NH:

1 OH wherein :0 means hydrogen or its substituents, such as halogen, orsulfo-groups, wlth compounds of the general formula HO3S- 1 OH wherein Rmeans hydrogen, alkyl aralk yl, aryl, alkylene, arylene or acidyl. S uchcom pounds are for instance the N-methyl,

N-ethyl, N-phenyl, N-benzyl, N-anisidyl, N-phenetidyl, N-cresidyl,N-salicylic, acid derivatives of the2-amino5-hydroxynaphthaline-7-sulfonic acid, further the2:2-dinaphthylamine 5 :5 dihydroxy-7 :7-disulfonic acid, and theproducts which are. ob

' furic acids, or from acids of the heterocyclic series, such ascyanuric acid, in which connection it may be remarkedthat polybasicacids may be united with one or several molecules of2-amino-5-hydroxynaphthaline-7-sulfonic chromium are derivatives nishes.

acid. As further acidyl derivativesthere may further be mentioned theproducts which are obtained by treatingthe;2-amino-5shydroxynaph-thaline-7-sulfonic acid with aromaticn1tro-compounds, such as nitrobenzoyl-chloride, reducing thecondensation products so obtained, and condensing same further withcompounds which may reactwith substances containing amino groups'Compounds of thesejdifferent species are described in great number inthe patent literature.

Particularly suitable asf'agents yielding of the trivalent chromium,such as chromiunr-hydroxide, chromium oxide, and thesaltsuwhich areformed from these compounds with acids.

' The products thus obtained are dyestuffs which may be employed for thedyeing of fibers of animal, vegetable and artificial origin, such aswool, silk, cotton, viscose; further for the manufacture of dyed var-These dyestuffs form dark colored powders which are soluble in water anddilute alkalies to blue to green-blue and blue-grey solutions. They areparticularly suitable. for the production of blue dyeings fast to light.

The following examples illustrate the invention:

v n Ewamplg 1 I 63 parts of the sodium salt of'tlie' dyestuff of theformula V Hols NmQ-Naw- I on on from 5-nitro-2-aminophenol andQ-phenylamino-5-naphthol-7-sulfonic acid (coupled under alkalineconditions) are dissolved in 3200 parts of hot water, the solution isneutralized and then mixed with 15.6 parts of Cr O in the form'of asolution of chromium fluoride of 7.8 percent. of strength; the whole isthen boiled ina reflux apparatus 951 for 24 to 30 hours. After cooling,the dyestuif formed separates in greater part; by addition of commonsalt the separation is completed. The isolateddyestufi 'is' a black ishpowder which dissolvesin water to a pure bath containing Glaubers saltblue tints havare boiled for 24 hours in the reflux apparamg goodpropertles of fastness. tus in 800 parts of Water with double the r ExamZ6 2 theoretical amount of Gr O -in the form of v i p chromium fluoride.By the additlon of com- '49.7 parts of the dyestufi of the formula monsalt thechromium complex whlch has been formed 1s separated and dined atmoderate temperature. It forms a dark blue powder which is easilysoluble 1n Water to a pure blue solution, dyeing wool and cotton bluetmts. 7 Y l The following tableshows the shades on obtained by couplmg,diazotized 5-n1tro-2 cotton or Viscose obtained with some of theamino-phenol with'2-benzoyl-am1no-5-naphcombinations accordmg to thepresent inven- -thol-7-sulfon1cac1d (coupled under alkaline t on:

Shade of the direct Diaz'otizing component Coupling component $335115 $11 pound I. 5-11itro-2-aminophenol'2-amino-5-hydroxynaphthaline-7-sulfonic acid Pure green-blue II.5'l1ltl'0'28111il10Ph81101 2-methylamino-5-hydroxynaphthaline-7-sulfonicacid Pure green-blue III. 5-nitro-2-aminophenol2-benzylaniino-fi-hydroxynaphthaline-7-sulfonic acid Pure green-blue IV.5-nitro-2-aminophenol 2-pl1enylaniino-5-hydroxynaphthaline-7-su1fonicacid Pure green-blue V.. 5-nitro-2-aminophenol2-p-phenetidin0-5-hydroxynaphthaline-7-sulfonic acid Pure green-blue VI.5-nitro-2-a1ninophenol I 2-O-anisidino-S-hydroxynaphthalinc-7-sulfonicacid Pure green-blue VII. o-nitro- -aminophenol 'l-g2-meth%xy-4-methyl)-phenylamino-5-hydroxynaphthaline-7-sul- Pure green-blue vI omc aci VIII. l-chloro-5-nitro-2-aminophenol 1- (IT-methoXy-M -methyl)-phenyl amino-5-liydroxyn aphth aline-7-sul- Purev green-blue 01110 2016l IX. 5-nitro-2-amiuophenol-4-sulfonic acid2-pl1enylamino-5-11ydroxynaplithaline-7-sulionicacid Pure green-blue X.31itro-4-ch1oro-2-am1nophenol-G-SulfOniO2-phenylamino-5-hydroxynaphthaline-7-sulfonic acid Pure green-blue aci vXI. 5-nitro-2-aminophenol 2-benzoylamino-5-hydroxynaphthaline-7-sulfonicacid Grey-blue XII. 5-nitro-2-am1nophenol.2-(3-amino-)-benzoylamino-S-hydroxynaphtlialine-7-sulfoi'iic acidGrey-blue XIII. 5nitr0-2-am 1nophono12-(3-nitro-)-benzoylamino-5-hydroxynaphthaline-7-sulfonic acid Gray-blueXIV. 5-nitro-2-ammophenol 2-gy-liydrolxyt carbonicacid)-plienyl-5-hydroxynaphthaline-7-sul- Blue 01110 2101 XV.Emitro-Z-aminophenol 2-acetylamino-5-hydroxynaphthaline-7-sulfonic acidBlue-grey XVI. 2 mols S-nitro-Z-aminophenol 5:5-dihydroxy-7:7-disulfonicacid-2:2-dinaphthyl urea Blue-grey ,XVII. 5-nitro-2-ami1 1ophenol2-p-toluenc-sulfamino-5 hydroxynaphthaline-7-sulionic acid Blue-greyXVIII. 5-nitro-2 am1nopl eno12(2-4-dinitro-)-phenylamino-5-hydroxynaphthaline-7-sulfonic acidBlue-grey XIX. 2 mols 5-mtro-2-amm0phenol2:2-ammodinaphthy1-5:5-dihydroxy-7 :7-disulfo11ic acid Blue5-nitro-2-aminophenol S- NH-(| ("1NH Blue conditions) are dissolved in6000 parts of The formula of the dyestufi No. V is:

blue solution; in caustic soda solution of 10' per cent. strength to agreenish blue solution; in concentrated sulfuric acid to a blue violetsolution. It dyes cotton in a neutral obtained by coupling diazotized5-nitro-2- amino-1-hydroxybenzene With the condensation product from2-amino-5-hydroxynaphthaline-7-sulfonic acid and chloro-acetic acid,

boiling water, and the solution is boiled for a long time in the refluxappartus With 15.2 parts of Cr O in the form of chromium fluoride. Thechromium compound of the dyestufl is thus precipitated. It is filteredand washed.

When it is dry it is a dark powder which dissolves somewhat sparingly inWater but easily in dilute sodium carbonate solution to a greenish bluesolution. It dyes cotton fast grey-blue tints in a solution alkalinewith sodium carbonate.

Example 3 46.1 parts by Weight of thedyestufi of the,

formula i S 03H The formula of the dyestuif N0, v11 is:

Hogs

HOaS

The formula ofthe' dyestufi No. XVII is:

NO N=N ta ta The formula. of the dyestuff. No. XVIII is:

. z Ho3s- NR NoaQlhN V a: H (i)H I wherein 00 means hydrogen or halogenor sulfo groups, and.R alkyl, alkylene, benzyl, phenyl,.

naphthyl, phenylene or an acidyl radicle of the aliphatic or of thebenzene series, With compounds of the trivalent chromium.

2. Processfor themanufacture of dyestufis containing chromium,consisting -in treating the herein described ohydroxy-azodyestuffs ofthe general formula Q T we em NOzQN=N on tn wherein av means hydrogen orhalogen, and

R alkyl, alkylene, benzyl, phenyl, naphthyl,

phenylene or an acidyl rad-icle of the aliphatic or of the benzeneseries, with com-i pounds of the trivalent chromium.

'3. Process for thema-nufacture of dye-V stuffs containing chromium,consisting in treating the herein described o-hydroxy-azodyestuffs ofthe general formula HOaS- N-R OH OH 'wherein R means alkyl, alkylene,benzyl, phenyl, naphthyl, phenylene or an acidyl radicle of thealiphatic or of the benzene series, with compounds of the trivalentchromium.

4:. Process for the manufacture of dyei stuffs containing chromium,consisting in treating the herein described o-hyd-roxy-a'zo dyestuffsofthe general formula f H Hois I i-R V No PQ -NQI- H tn" wherein R meansa radicle which contains a benzene or naphthalene nucleus, with com:pounds of the trlvalent'chromium.

5. Process for the manufacture of dye I V stuffs containing chromium,consisting in treating the herein described o-hydroxy-azodyestuffs ofthe general formula wherein R means a phenyl or naphthyl radi ole, withcompoundsof the trivalent chromium. i

6. Process for the manufacture of dyestufis containing chromium,consisting in treating the herein describedo.-hydroxy-azo-- dyestuffs ofthe general formula r wherein R means a phenyl radicle, with compoundsofthe trivalent chromium. 7

7. Process for the manufacture 'of dyestuffs containing chromium,consisting in treating the herein described, o-hydroXy-az'o5 dyestufi ofthe formula with compounds of the trivalent chromium. 8. As new productsthe herein described dyestuffs containing chromium obtained by treatingthe o-hydroxy-azo-dyestuffsof the general formula wherein'w meanshydrogen or halogen or sul'fo groups, and R alkyl, alkylene, benzyl,

phenyl, naphthyl, phenylene or an aci'dylf radicle of the aliphatic orof the benzene series with compounds of the trivalentcl romium',whichdyestufls form dark colored powders which are soluble in water anddilute alkalies to blue to grey-blue solutions, dyeing fibers of animal,vegetable and artificial origin, and. varnishes, blue to grey tints.

9. As new products the herein described dyestuffs containing chromiumobtained by treating the o-hydroxy-azo-dyestufis of the the trivalentchromium, which dyestuffs form 'miumpwhich dyestuffs form dark colored AI as:

general formula wherein as means hydrogen or halogen, and R alkyl,alkylene, benzyl, phenyl, naphthyl, phenylene or an acidyl radicle ofthe aliphatic or of the benzene series with compounds of dark coloredpowders which are soluble in water and dilute alkalies to blue togrey-blue solutions, dyeing fibers of animal, vegetable and artificialorigin, and varnishes, blue to grey tints.

' 10. As new'products the herein described dyestuffs containing chromiumobtained by treating the o-hydroXy-azo-dyestuffs of the general formulaV wherein R means alkyl, alkylene, benzyl,

phenyl, naphthyl, ph-enyl-ene or an acidyl radicle of the aliphatic orof the benzene series with compounds of the-trivalent chropowders whichare soluble in water and dilute alkalies to blue to grey-blue solutions,dyeing fibers of animal, vegetable and artificial origin, and varnishes,blue to grey tints.

11. As new products theherein described dyestufis containing chromiumobtained by treating the o-hydroXy-azo-dyestufl's of'the general formulato blue to grey-blue solutions, dyeing fibers of animals, vegetable andartificial origin, and varnishes, blue to grey tints.

' 12.;As new products the herein described dyestufls containing chromiumobtained by general formula treating theo-hydroxy-azo-dyestufi's "of thewherein means a phenyl or naphthyl radi- I v cle with compounds of thetrivalent chromium, which dyestufls form dark colored powderswhich aresoluble in water and dilute alkalies to blue to grey-blue solutions,dyeing fibers of animal, vegetable and artificial origin, and varnishes,blue to grey tints.

13. As new products the herein described dyestuffs containing chromiumobtained-by treating the o-hydroxy-azo-dyestufls of'the general formulaV V pounds of the trivalent chromium, which dyestufls form dark coloredpowders which are soluble in water and dilute alkalies to blue togrey-blue solutions,jdyeing.fibers of animal, vegetable and artificialorigin, and van nishes, blueto grey tints.

14. As new productsthe herein described dyestuffs containingchromium-obtained by} treating the o-hydroxy-azo-dyestuffs of theformula v OH v with compounds of the trivalent chromium which dyestuffsform dark colored powders which are soluble in water and dilute alkaliesto blue solutions, dyeing fibers of animal, vegetable and artificialorigin, and varnishes,

blue tints.

In witness wherof we ,have hereunto signed our names this31st day ofMarch 192e, V i g I V FRITZSTRAUB. l ALTER ANDERAU. HANS MAYER.

, V 9o wherem R means a phenyl nucleus wlth com-

